CN113275000B - High-temperature-resistant cerium-zirconium composite oxide and preparation method and application thereof - Google Patents
High-temperature-resistant cerium-zirconium composite oxide and preparation method and application thereof Download PDFInfo
- Publication number
- CN113275000B CN113275000B CN202110834188.XA CN202110834188A CN113275000B CN 113275000 B CN113275000 B CN 113275000B CN 202110834188 A CN202110834188 A CN 202110834188A CN 113275000 B CN113275000 B CN 113275000B
- Authority
- CN
- China
- Prior art keywords
- cerium
- composite oxide
- zirconium composite
- slurry
- zirconium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 137
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 57
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 16
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 105
- 238000001556 precipitation Methods 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 21
- 230000032683 aging Effects 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 10
- 150000000703 Cerium Chemical class 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 7
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 150000003754 zirconium Chemical class 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 28
- 238000010335 hydrothermal treatment Methods 0.000 description 16
- 239000012266 salt solution Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000012065 filter cake Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003828 vacuum filtration Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 6
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 5
- 229910002637 Pr6O11 Inorganic materials 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 4
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 3
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 2
- 229960001633 lanthanum carbonate Drugs 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 2
- RNAMYOYQYRYFQY-UHFFFAOYSA-N 2-(4,4-difluoropiperidin-1-yl)-6-methoxy-n-(1-propan-2-ylpiperidin-4-yl)-7-(3-pyrrolidin-1-ylpropoxy)quinazolin-4-amine Chemical compound N1=C(N2CCC(F)(F)CC2)N=C2C=C(OCCCN3CCCC3)C(OC)=CC2=C1NC1CCN(C(C)C)CC1 RNAMYOYQYRYFQY-UHFFFAOYSA-N 0.000 description 1
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- HFNQLYDPNAZRCH-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O.OC(O)=O HFNQLYDPNAZRCH-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UTWHRPIUNFLOBE-UHFFFAOYSA-H neodymium(3+);tricarbonate Chemical compound [Nd+3].[Nd+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O UTWHRPIUNFLOBE-UHFFFAOYSA-H 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- XIRHLBQGEYXJKG-UHFFFAOYSA-H praseodymium(3+);tricarbonate Chemical compound [Pr+3].[Pr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XIRHLBQGEYXJKG-UHFFFAOYSA-H 0.000 description 1
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 1
- -1 rare earth salt Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a cerium-zirconium composite oxide, in particular to a high-temperature-resistant cerium-zirconium composite oxide and a preparation method and application thereof. A cerium-zirconium composite oxide containing a cerium oxide, a zirconium oxide, and an oxide of at least one rare earth metal element selected from the group consisting of cerium and other elements; after the cerium-zirconium composite oxide is aged and heat-treated at 1100 ℃ for 5 hours, the content of the doped rare earth elements on the surface of the cerium-zirconium composite oxide is reduced, unchanged or increased compared with the content of the doped rare earth elements in a fresh state, and the increase amplitude is not more than 5%. The cerium-zirconium composite oxide provided by the invention has excellent high-temperature stability and good catalytic performance.
Description
Technical Field
The invention relates to a cerium-zirconium composite oxide, in particular to a high-temperature-resistant cerium-zirconium composite oxide and a preparation method and application thereof.
Background
Automobile exhaust, especially CO, CHx and NO in exhaustxIt has great harm to human life and natural environment. Noble metal catalyst as the most mature and effective automobile exhaust purification deviceCan simultaneously purify CO, CHx and NO in the tail gasx. Exhaust gas purification is mainly achieved by the interaction between a noble metal (e.g., Pt, Rh, Pd) and a cerium-zirconium composite oxide in which the noble metal is dispersed. As a material for dispersing the noble metal, the cerium-zirconium composite oxide is required to have a large specific surface area and excellent high-temperature stability, otherwise when subjected to high temperatures of automobile exhaust, the noble metal is easily embedded by a sharp decrease in specific surface area, resulting in a decrease in catalytic activity.
The cerium-zirconium composite oxide has high temperature stability, namely a stable single crystal phase is still kept after high-temperature aging, the grain size can be kept in a small range, and meanwhile, the specific surface area, the pore volume and the proper pore channel structure can be kept high.
Disclosure of Invention
The literature reports that the high-temperature stability of the cerium-zirconium composite oxide can be improved by introducing a third component rare earth element into the cerium-zirconium composite oxide. The inventor researches and discovers that after high-temperature aging, particularly at the temperature of 1000-1100 ℃, compared with the cerium-zirconium composite oxide which is not subjected to high-temperature aging (called as a fresh state, the same below), the surface content of the doped rare earth element in the cerium-zirconium composite oxide can be greatly increased; in other words, the doped rare earth element is precipitated from the cerium-zirconium composite oxide to the surface, so that the high-temperature stability of the cerium-zirconium composite oxide is reduced, and the catalytic performance of the cerium-zirconium composite oxide is also reduced. Based on this finding, the present inventors have proposed that the high temperature stability can be improved by controlling the content of the doped rare earth element on the surface of the cerium-zirconium composite oxide after aging at high temperature.
A cerium-zirconium composite oxide comprising a cerium oxide, a zirconium oxide, and at least one oxide of a rare earth metal element other than cerium; after the cerium-zirconium composite oxide is aged and heat-treated at 1100 ℃ for 5 hours, the content of the doped rare earth elements on the surface of the cerium-zirconium composite oxide is reduced, unchanged or increased compared with the content of the doped rare earth elements in a fresh state, and the increase amplitude is not more than 5%.
Herein, the fresh state refers to a cerium-zirconium composite oxide which has not been subjected to high-temperature aging. That is, it is usually a cerium-zirconium composite oxide obtained by calcining at 500-800 ℃ for 3-6 hours.
In some embodiments, the doped rare earth element content at the surface of the cerium-zirconium composite oxide increases by 0 to 5% compared to the fresh state after the cerium-zirconium composite oxide is subjected to an aging heat treatment at 1100 ℃ for 5 hours.
In some embodiments, the cerium-zirconium composite oxide has a specific surface area of 60m or more after aging heat treatment at 1000 ℃ for 5 hours2G and/or pore volume of 0.45cm or more3/g。
In some embodiments, the cerium-zirconium composite oxide has a specific surface area of 30m or more after aging heat treatment at 1100 ℃ for 5 hours2G and/or pore volume of 0.25cm or more3/g。
In some embodiments, the cerium-zirconium composite oxide has a grain size of 12nm or less after aging heat treatment at 1100 ℃ for 5 hours.
In some embodiments, the cerium-zirconium composite oxide has a static oxygen storage amount of more than or equal to 600 [ mu ] mol O after aging heat treatment at 1100 ℃ for 5 hours2/g。
The rare earth metals described herein do not include cerium.
In some embodiments, the rare earth metal element other than cerium is one or a combination of more than one of lanthanum, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium; optionally, one or more of lanthanum, yttrium, praseodymium and neodymium.
In some embodiments, the cerium-zirconium composite oxide has a content of doped rare earth elements of 0 to 30wt% on the surface of the cerium-zirconium composite oxide after aging heat treatment at 1100 ℃ for 5 hours.
In some embodiments, the cerium-zirconium composite oxide has the following surface element contents after aging heat treatment at 1100 ℃ for 5 hours:
25-50 wt% of cerium element;
20-65 wt% of zirconium element;
0-10wt% of lanthanum element;
0-10wt% of yttrium element;
0-20wt% of neodymium element;
0-20wt% of praseodymium element.
In some embodiments, the cerium-zirconium composite oxide has a surface content of 0 to 30wt% of the doped rare earth element in a fresh state.
In some embodiments, the cerium zirconium composite oxide has the following surface element contents in a fresh state:
25-50 wt% of cerium element;
20-65 wt% of zirconium element;
0-10wt% of lanthanum element;
0-10wt% of yttrium element;
0-20wt% of neodymium element;
0-20wt% of praseodymium element.
In some embodiments, the cerium-zirconium composite oxide contains:
10-65 wt% of cerium oxide;
25wt% to 80wt% zirconia;
1 to 20% by weight of at least one oxide of a rare earth metal element other than cerium.
Optionally, the cerium-zirconium composite oxide contains:
30-60 wt% of cerium oxide;
30-70 wt% of zirconia;
3 to 15wt% of at least one oxide of a rare earth metal element other than cerium.
Herein, the high temperature refers to 1000-1100 ℃, and the low temperature refers to 500-800 ℃.
The invention also provides a preparation method of the cerium-zirconium composite oxide, and the cerium-zirconium composite oxide can be prepared by adopting the method.
A method for preparing a cerium-zirconium composite oxide, comprising:
(a) first-step precipitation: dissolving corresponding rare earth element salt in mass of oxide in pure water, and then carrying out contact reaction on the obtained solution and excessive alkali liquor to obtain precipitation slurry A of the rare earth element;
(b) the first step is hydrothermal: carrying out hydrothermal reaction on the obtained precipitation slurry A to obtain slurry B;
(c) and a second step of precipitation: dissolving cerium salt and zirconium salt corresponding to the mass of oxides in pure water, and carrying out contact reaction with the obtained slurry B to obtain a precipitate slurry C;
(d) the second step is hydrothermal: carrying out hydrothermal reaction on the obtained precipitation slurry C to obtain slurry D; and adding a surfactant into the slurry D, fully stirring, and then carrying out solid-liquid separation, washing and roasting to obtain the cerium-zirconium composite oxide.
In the above method for producing a cerium-zirconium composite oxide, the rare earth element does not include cerium.
The research of the inventor finds that firstly, the salt of the rare earth element is precipitated and subjected to hydrothermal reaction to prepare slurry, then the slurry is contacted with cerium salt and zirconium salt to react to obtain precipitated slurry, and then the hydrothermal reaction is carried out, so that on one hand, the precipitation sequence is changed, the rare earth element can be inhibited from being separated out from the cerium-zirconium composite oxide, and the high-temperature stability and the catalytic performance of the composite oxide can be obviously improved; on the other hand, through hydrothermal reaction, the crystal grains of the cerium-zirconium composite oxide can be well grown in the initial stage, the grain boundary energy is reduced, so that good thermal stability is kept, and meanwhile, under the condition of high pressure, the doped rare earth elements can well enter the cerium-zirconium crystal lattice to form the composite oxide, so that the high-temperature stability of the composite oxide is improved. And further, after the prepared cerium-zirconium composite oxide is aged at the high temperature of 1000-1100 ℃, the doped rare earth elements are not easy to be separated out on the surface, and the high-temperature stability of the cerium-zirconium composite oxide is improved.
In some embodiments, the salt of the rare earth element is selected from a nitrate (nitrate), a chloride (chloride), or a carbonate (carbonate) of the rare earth element.
In some embodiments, the base is selected from one or a combination of more than one of sodium hydroxide, potassium hydroxide, ammonium bicarbonate, and ammonia. Generally, the amount of the alkali solution is sufficient to ensure that the cerium salt, the zirconium salt and the rare earth salt are remained after the complete reaction to maintain the whole system to be alkaline.
In some embodiments, the first precipitation step may be performed by forward precipitation (by adding a base solution to a salt solution), reverse precipitation (by adding a salt solution to a base solution), and co-current precipitation (by adding a salt solution and a base solution simultaneously to the reactor; stirring is continued during precipitation to ensure that the reaction is sufficiently carried out; in some embodiments, the temperature of the first precipitation step is 30-80 ℃.
In some embodiments, the temperature of the first step hydrothermal is 90-220 ℃ and the time is 6-48 h; preferably, the temperature of the first step hydrothermal process is 120-210 ℃, and the time is 8-16 h.
In some embodiments, the cerium and zirconium salts in the second precipitation step are selected from nitrates, chlorides, or carbonates thereof. Stirring is preferably continued during the second precipitation step to ensure that the reaction is fully carried out.
In some embodiments, the valence of cerium in the cerium salt may be +3 or +4, and when the +3 cerium salt is selected, an oxidant may be added to the salt solution to oxidize the cerium salt to +4, such as aqueous hydrogen peroxide.
In some embodiments, when the oxidizing agent is added to the +3 valent cerium salt solution, it is added in an amount of Ce on a molar basis3+0.5-2.5 times of ions.
In some embodiments, the temperature of the second step hydrothermal is 90-250 ℃ and the time is 6-48 h; preferably, the hydrothermal temperature is 150 ℃ and 220 ℃, and the time is 8-24 h.
In some embodiments, the surfactant added to slurry D is selected from cationic surfactants, anionic surfactants, nonionic surfactants, polyethylene glycols, carboxylic acids and salts thereof, surfactants containing carboxymethylated fatty alcohol ethoxylates; preferably, the surfactant is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, polyethylene glycol and lauric acid. The amount of the surfactant is preferably 30 to 80% by mass of the cerium-zirconium composite oxide to be prepared.
In some embodiments, the temperature of the calcination is 500-800 ℃, and the calcination time is 3-6 h. The firing atmosphere may be an air atmosphere.
In the above method for preparing the cerium-zirconium composite oxide, both the first hydrothermal step and the second hydrothermal step can be carried out in an autoclave.
The invention also provides a catalyst prepared from the cerium-zirconium composite oxide.
The invention also provides application of the catalyst prepared from the cerium-zirconium composite oxide, and the catalyst can be applied to purification of motor vehicle tail gas, catalytic combustion of natural gas, purification treatment of organic waste gas and denitration treatment of industrial waste gas.
After the cerium-zirconium composite oxide provided by the embodiment of the invention is subjected to heat treatment at 1100 ℃ for 5 hours, the content of surface elements is analyzed by XPS, the doped rare earth elements are reduced or slightly increased compared with a fresh state, the increase amplitude is not more than 5%, and the cerium-zirconium composite oxide has excellent high-temperature stability. The cerium-zirconium and rare earth element composite oxide provided by the embodiment of the invention still has a thickness of more than 30m after being subjected to heat treatment at 1100 ℃ for 5 hours2Specific surface area per gram and good ageing resistance. The cerium-zirconium composite oxide provided by the embodiment of the invention also has good catalytic performance.
Drawings
Fig. 1 is an XRD diffractogram of the cerium-zirconium composite oxide of example 1 of the present invention.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
The invention uses the following method to measure various performances and indexes:
(1) surface element content
The content of surface elements was measured by XPS (X-ray photoelectron spectroscopy). After the sample to be tested is placed in the sample chamber, it is excited by a beam of monochromatic X-rays. The energy of the photon is larger than the binding energy of the electron of a certain atomic orbit in the sample, so that the electron can be excited to leave the current orbit, and the photoelectron with certain kinetic energy is obtained. And collecting the obtained photoelectrons and amplifying signals to obtain the XPS spectrogram. The electron binding energy of different orbitals of each atom is constant and has a labeling property, so that the element can be quantitatively analyzed by XPS.
(2) Specific surface area
The test of specific surface area refers to the BET specific surface as determined by nitrogen adsorption. The sample is pretreated for 1 hour at 300 ℃, the sample tube is soaked in liquid nitrogen (-196 ℃) for adsorption test, and desorption test is carried out at room temperature (25 ℃). The result is S(T,h)Wherein (T, h) means heat treatment at T temperature for h time. The analysis of the specific surface area was carried out using a Micromeritics TriStar model II fully automatic adsorption apparatus from Mac instruments USA.
(3) Pore volume (pore volume)
The pore volume analysis was performed using a Micromeritics TriStar model II fully automated adsorption apparatus from Mac instruments USA. The barrett, georgena and hurned (BJH) method with Harkins-Jura law (Harkins-Jura law) was used for determining mesoporosity (Barett, Joyner and halonda method). Results are expressed as V(T,h)Wherein (T, h) means heat treatment at T temperature for h time.
(4) Grain size D
The analysis was carried out using a German Bruker D8 Advance X-ray diffractometer and the XRD pattern obtained was calculated for grain size using the Debye-Scherrer formula.
(5) Static oxygen storage OSC
The oxygen storage amount of the cerium-zirconium composite oxide was analyzed by using a ChemBET-3000 instrument of Quantachrome corporation.
Example 1
The cerium-zirconium composite oxide comprises the following components in percentage by mass: 50% CeO2、40%ZrO2、4%La2O3、4%Y2O3、2%Nd2O3。
The preparation method of the cerium-zirconium composite oxide of the embodiment is as follows:
(a) first-step precipitation: dissolving 10.64g of lanthanum nitrate, 13.56g of yttrium nitrate and 5.21g of neodymium nitrate by using pure water, then slowly adding excessive sodium hydroxide solution into the rare earth salt solution at the temperature of 30 ℃, and continuously stirring in the whole process to ensure that the reaction is fully carried out; obtaining a precipitation slurry A of rare earth elements
(b) The first step is hydrothermal: transferring the precipitate slurry A obtained by the reaction into a high-pressure kettle for hydrothermal treatment, wherein the hydrothermal temperature is 120 ℃, the hydrothermal time is 12 hours, and obtaining slurry B after the hydrothermal treatment is finished;
(c) and a second step of precipitation: 111.12g of cerium (III) chloride and 111.74g of zirconium oxychloride were dissolved in pure water, and 0.5 mol-fold amount of Ce was added thereto after completion of the dissolution3+Oxidizing the aqueous solution of hydrogen peroxide, slowly adding the oxidized aqueous solution of hydrogen peroxide into the slurry B, and continuously stirring the slurry B in the whole process to obtain a precipitate slurry C;
(d) the second step is hydrothermal: placing the precipitate slurry C in the high-pressure kettle again for hydrothermal reaction at 150 ℃ for 8h to obtain slurry D after the reaction is finished;
and adding 30g of cationic surfactant cetyl trimethyl ammonium bromide into the slurry D, fully stirring, carrying out solid-liquid separation by vacuum filtration after stirring is finished, washing the obtained filter cake by pure water, and roasting for 3 hours at 500 ℃ in an air atmosphere to obtain the fresh cerium-zirconium composite oxide.
And respectively carrying out heat treatment on the obtained fresh cerium-zirconium composite oxide at 1000 ℃ and 1100 ℃ for 5h to obtain the aged cerium-zirconium composite oxide.
Example 2
The cerium-zirconium composite oxide comprises the following components in percentage by mass: 30% CeO2、65%ZrO2、5%La2O3。
(a) First-step precipitation: dissolving 11.45g of lanthanum chloride by using pure water, then slowly adding a rare earth salt solution into an excessive potassium hydroxide solution at the temperature of 45 ℃, and continuously stirring in the whole process to ensure that the reaction is fully carried out; obtaining a precipitation slurry A of rare earth elements
(b) The first step is hydrothermal: transferring the precipitate slurry A obtained by the reaction into a high-pressure kettle for hydrothermal treatment, wherein the hydrothermal temperature is 160 ℃, the hydrothermal time is 8 hours, and obtaining slurry B after hydrothermal treatment;
(c) and a second step of precipitation: 66.67g of cerium (III) chloride and 200g of zirconyl nitrate were dissolved in pure water, and 1.0 mol-fold Ce was added thereto3+Oxidizing the aqueous solution of hydrogen peroxide, slowly adding the oxidized aqueous solution of hydrogen peroxide into the slurry B, and continuously stirring the slurry B in the whole process to obtain a precipitate slurry C;
(d) the second step is hydrothermal: placing the precipitate slurry C in the high-pressure kettle again for hydrothermal reaction at 180 ℃ for 12h to obtain slurry D after the reaction is finished;
and adding 50g of hexadecyl trimethyl ammonium bromide into the slurry D, fully stirring, carrying out solid-liquid separation by vacuum filtration after stirring is finished, washing the obtained filter cake by using pure water, and roasting for 3 hours at 600 ℃ in an air atmosphere to obtain a fresh composite oxide.
And respectively carrying out heat treatment on the obtained fresh cerium-zirconium composite oxide at 1000 ℃ and 1100 ℃ for 5h to obtain the aged cerium-zirconium composite oxide.
Example 3
The cerium-zirconium composite oxide comprises the following components in percentage by mass: 40% CeO2、50%ZrO2、3%La2O3、2%Y2O3、5%Pr6O11。
(a) First-step precipitation: dissolving 8.43g of lanthanum carbonate, 6.33g of yttrium carbonate and 12.82g of praseodymium nitrate by using pure water, then slowly adding a rare earth salt solution and excessive ammonia water into a reactor in parallel flow at the temperature of 60 ℃, and continuously stirring in the whole process to ensure that the reaction is fully carried out; obtaining a precipitation slurry A of rare earth elements
(b) The first step is hydrothermal: transferring the precipitate slurry A obtained by the reaction into a high-pressure kettle for hydrothermal treatment, wherein the hydrothermal temperature is 180 ℃, the hydrothermal time is 16h, and obtaining slurry B after the hydrothermal treatment is finished;
(c) and a second step of precipitation: 123.46g of ceric ammonium nitrate (IV) and 67.98g of zirconium carbonate are dissolved by pure water, and then the dissolved substances are slowly added into the slurry B, and the whole process is continuously stirred to obtain a precipitate slurry C;
(d) the second step is hydrothermal: placing the precipitate slurry C in the high-pressure kettle again for hydrothermal reaction at 180 ℃ for 16h to obtain slurry D after the reaction is finished;
and adding 40g of sodium dodecyl sulfate into the slurry D, fully stirring, carrying out solid-liquid separation by vacuum filtration after stirring is finished, washing the obtained filter cake by pure water, and roasting at 800 ℃ for 4 hours in an air atmosphere to obtain a fresh cerium-zirconium composite oxide.
And respectively carrying out heat treatment on the obtained fresh cerium-zirconium composite oxide at 1000 ℃ and 1100 ℃ for 5h to obtain the aged cerium-zirconium composite oxide.
Example 4
The cerium-zirconium composite oxide comprises the following components in percentage by mass: 40% CeO2、55%ZrO2、5%Nd2O3。
(a) First-step precipitation: dissolving 10.89g of neodymium chloride by pure water, then slowly adding a rare earth salt solution and excessive ammonium bicarbonate into a reactor in a parallel flow manner at the temperature of 80 ℃, and continuously stirring in the whole process to ensure that the reaction is fully carried out; obtaining a precipitation slurry A of rare earth elements
(b) The first step is hydrothermal: transferring the precipitate slurry A obtained by the reaction into a high-pressure kettle for hydrothermal treatment, wherein the hydrothermal temperature is 210 ℃, the hydrothermal time is 12 hours, and obtaining slurry B after the hydrothermal treatment is finished;
(c) and a second step of precipitation: 111.16g of ammonium carbonate (III) and 153.63g of zirconium oxychloride were dissolved in pure water, and 2.0 times by mol of Ce was added thereto3+Oxidizing the aqueous solution of hydrogen peroxide, slowly adding the oxidized aqueous solution of hydrogen peroxide into the slurry B, and continuously stirring the slurry B in the whole process to obtain a precipitate slurry C;
(d) the second step is hydrothermal: placing the precipitate slurry C in the high-pressure kettle again for hydrothermal reaction at 210 ℃ for 24h to obtain slurry D after the reaction;
and adding 60g of polyethylene glycol into the slurry D, fully stirring, carrying out solid-liquid separation by vacuum filtration after stirring is finished, washing the obtained filter cake by using pure water, and roasting at 700 ℃ for 6 hours in an air atmosphere to obtain a fresh cerium-zirconium composite oxide.
And respectively carrying out heat treatment on the obtained fresh cerium-zirconium composite oxide at 1000 ℃ and 1100 ℃ for 5h to obtain the aged cerium-zirconium composite oxide.
Example 5
The cerium-zirconium composite oxide comprises the following components in percentage by mass: 60% CeO2、30%ZrO2、2%La2O3、2%Y2O3、4%Nd2O3、2%Pr6O11。
(a) First-step precipitation: dissolving 4.58g of lanthanum chloride, 5.39g of yttrium chloride, 10.42g of neodymium nitrate and 4.45g of praseodymium chloride by using pure water, then slowly adding a rare earth salt solution into potassium hydroxide at the temperature of 50 ℃, and continuously stirring in the whole process to ensure that the reaction is fully carried out; obtaining a precipitation slurry A of rare earth elements
(b) The first step is hydrothermal: transferring the precipitate slurry A obtained by the reaction into a high-pressure kettle for hydrothermal treatment, wherein the hydrothermal temperature is 180 ℃, the hydrothermal time is 10 hours, and obtaining slurry B after the hydrothermal treatment is finished;
(c) and a second step of precipitation: 152.28g of cerium (III) nitrate and 92.31g of zirconyl nitrate were dissolved in pure water, and 2.5 times by mol of Ce was added thereto after completion of the dissolution3+Oxidizing the aqueous solution of hydrogen peroxide, slowly adding the oxidized aqueous solution of hydrogen peroxide into the slurry B, and continuously stirring the slurry B in the whole process to obtain a precipitate slurry C;
(d) the second step is hydrothermal: placing the precipitate slurry C in the high-pressure kettle again for hydrothermal reaction at 200 ℃ for 10h to obtain slurry D after the reaction is finished;
and adding 80g of lauric acid into the slurry D, fully stirring, carrying out solid-liquid separation by vacuum filtration after stirring is finished, washing the obtained filter cake by pure water, and roasting at 600 ℃ for 5 hours in an air atmosphere to obtain a fresh cerium-zirconium composite oxide.
And respectively carrying out heat treatment on the obtained fresh cerium-zirconium composite oxide at 1000 ℃ and 1100 ℃ for 5h to obtain the aged cerium-zirconium composite oxide.
Example 6
The cerium-zirconium composite oxide comprises the following components in percentage by mass: 30% CeO2、60%ZrO2、5%La2O3、2%Nd2O3、3%Pr6O11。
(a) First-step precipitation: dissolving 13.30g of lanthanum nitrate, 5.57g of neodymium carbonate and 5.34g of praseodymium carbonate by using pure water, slowly adding ammonia water into a salt solution at the temperature of 70 ℃, and continuously stirring in the whole process to ensure that the reaction is fully carried out; obtaining a precipitation slurry A of rare earth elements
(b) The first step is hydrothermal: transferring the precipitate slurry A obtained by the reaction into a high-pressure kettle for hydrothermal treatment, wherein the hydrothermal temperature is 150 ℃, the hydrothermal time is 15h, and obtaining slurry B after the hydrothermal treatment is finished;
(c) and a second step of precipitation: 76.14g of cerium (III) nitrate and 167.59g of zirconium oxychloride were dissolved in pure water, and 1.5 times by mol of Ce was added after completion of the dissolution3+Oxidizing the aqueous solution of hydrogen peroxide, slowly adding the oxidized aqueous solution of hydrogen peroxide into the slurry B, and continuously stirring the slurry B in the whole process to obtain a precipitate slurry C;
(d) the second step is hydrothermal: placing the precipitate slurry C in the high-pressure kettle again for hydrothermal reaction at the reaction temperature of 170 ℃ for 20 hours to obtain slurry D after the reaction is finished;
and adding 70g of lauric acid into the slurry D, fully stirring, carrying out solid-liquid separation by vacuum filtration after stirring is finished, washing the obtained filter cake by pure water, and roasting at 500 ℃ for 6 hours in an air atmosphere to obtain a fresh cerium-zirconium composite oxide.
And respectively carrying out heat treatment on the obtained fresh cerium-zirconium composite oxide at 1000 ℃ and 1100 ℃ for 5h to obtain the aged cerium-zirconium composite oxide.
Example 7
The cerium-zirconium composite oxide comprises the following components in percentage by mass: 45% CeO2、50%ZrO2、3%Y2O3、2%Pr6O11。
(a) First-step precipitation: dissolving 10.17g of yttrium nitrate and 5.13g of praseodymium nitrate by using pure water, then slowly adding a salt solution into an ammonium bicarbonate solution at the temperature of 30 ℃, and continuously stirring in the whole process to ensure that the reaction is fully carried out; obtaining a precipitation slurry A of rare earth elements
(b) The first step is hydrothermal: transferring the precipitate slurry A obtained by the reaction into a high-pressure kettle for hydrothermal treatment, wherein the hydrothermal temperature is 210 ℃, the hydrothermal time is 8 hours, and obtaining slurry B after hydrothermal treatment;
(c) and a second step of precipitation: 138.89g of ceric ammonium nitrate (V) and 67.97g of zirconium carbonate are dissolved by pure water, and then the dissolved substances are slowly added into the slurry B, and the whole process is continuously stirred to obtain a precipitation slurry C;
(d) the second step is hydrothermal: placing the precipitate slurry C in the high-pressure kettle again for hydrothermal reaction at 160 ℃ for 24h to obtain slurry D after the reaction;
and adding 50g of polyethylene glycol into the slurry D, fully stirring, carrying out solid-liquid separation by vacuum filtration after stirring is finished, washing the obtained filter cake by using pure water, and roasting at 800 ℃ for 3 hours in an air atmosphere to obtain a fresh cerium-zirconium composite oxide.
And respectively carrying out heat treatment on the obtained fresh cerium-zirconium composite oxide at 1000 ℃ and 1100 ℃ for 5h to obtain the aged cerium-zirconium composite oxide.
Example 8
The cerium-zirconium composite oxide comprises the following components in percentage by mass: 55% CeO2、35%ZrO2、5%La2O3、5%Nd2O3。
(a) First-step precipitation: dissolving 14.04g of lanthanum carbonate and 10.89g of neodymium chloride by using pure water, then slowly adding a salt solution and a sodium hydroxide solution into a reactor in parallel flow at the temperature of 65 ℃, and continuously stirring in the whole process to ensure that the reaction is fully carried out; obtaining a precipitation slurry A of rare earth elements
(b) The first step is hydrothermal: transferring the precipitate slurry A obtained by the reaction into a high-pressure kettle for hydrothermal treatment, wherein the hydrothermal temperature is 120 ℃, the hydrothermal time is 16h, and obtaining slurry B after the hydrothermal treatment is finished;
(c) and a second step of precipitation: 152.85g of cerium carbonate(III) 97.76g of zirconium oxychloride was dissolved in pure water, and 2.0 times by mole of Ce was added thereto after completion of the dissolution3+Oxidizing the aqueous solution of hydrogen peroxide, slowly adding the oxidized aqueous solution of hydrogen peroxide into the slurry B, and continuously stirring the slurry B in the whole process to obtain a precipitate slurry C;
(d) the second step is hydrothermal: placing the precipitate slurry C in the high-pressure kettle again for hydrothermal reaction at 150 ℃ for 24h to obtain slurry D after the reaction is finished;
and adding 40g of lauric acid into the slurry D, fully stirring, carrying out solid-liquid separation by vacuum filtration after stirring is finished, washing the obtained filter cake by pure water, and roasting at 700 ℃ for 4 hours in an air atmosphere to obtain a fresh cerium-zirconium composite oxide.
And respectively carrying out heat treatment on the obtained fresh cerium-zirconium composite oxide at 1000 ℃ and 1100 ℃ for 5h to obtain the aged cerium-zirconium composite oxide.
Comparative example 1
The cerium-zirconium composite oxide comprises the following components in percentage by mass: 40% CeO2、50%ZrO2、3%La2O3、3%Y2O3、2% Nd2O3、2%Pr6O11。
The preparation method of the cerium-zirconium composite oxide of the comparative example comprises the following steps: 101.52g of cerium (III) nitrate, 153.84g of zirconyl nitrate, 8.01g of lanthanum nitrate, 10.17g of yttrium nitrate, 5.21g of neodymium nitrate, and 5.13g of praseodymium nitrate were weighed out, dissolved in pure water, and 2.0 times by mole of Ce was added3+Oxidizing the aqueous solution of hydrogen peroxide, slowly adding the salt solution into excessive ammonia water at 70 ℃, continuously stirring in the whole process to ensure that the reaction is fully carried out, adding 50g of hexadecyl trimethyl ammonium bromide into the slurry after the precipitation is finished, fully stirring, placing the obtained slurry into a constant-temperature water bath at 90 ℃ for aging, wherein the aging time is 8h, carrying out solid-liquid separation on the slurry after the aging is finished, washing the obtained filter cake with pure water, and roasting at 600 ℃ for 3h in the air atmosphere to obtain the fresh cerium-zirconium composite oxide. The obtained fresh cerium-zirconium composite oxide is subjected to heat treatment at 1000 ℃ and 1100 ℃ for 5 hours to obtain the aged cerium-zirconium composite oxideThe cerium-zirconium mixed oxide of (1).
Comparative example 2
The cerium-zirconium composite oxide comprises the following components in percentage by mass: 35% CeO2、60%ZrO2、3%Y2O3、2%Nd2O3。
The preparation method of the cerium-zirconium composite oxide of the comparative example comprises the following steps: 108.02g of ammonium ceric nitrate (IV) and 184.62g of zirconyl nitrate pure water are dissolved, potassium hydroxide and a salt solution are slowly added into the reactor in a parallel flow manner at the temperature of 60 ℃ after the dissolution is finished, and the whole process is continuously stirred to ensure that the reaction is fully carried out. And after the precipitation is finished, placing the slurry into a high-pressure reaction kettle for hydrothermal reaction, and reacting at the temperature of 180 ℃ for 24 hours to obtain precipitation slurry A.
Dissolving 10.17g of yttrium nitrate and 4.36g of neodymium chloride by using pure water, slowly adding the dissolved yttrium nitrate and the dissolved neodymium chloride into the precipitation slurry A in the previous step after the dissolution is finished, continuously stirring the whole process to ensure that the reaction is fully carried out, then carrying out solid-liquid separation on the slurry, washing the obtained filter cake by using the pure water, and roasting the washed filter cake for 4 hours at the temperature of 800 ℃ in the air atmosphere to obtain the fresh cerium-zirconium composite oxide. And carrying out heat treatment on the obtained fresh cerium-zirconium composite oxide at 1000 ℃ and 1100 ℃ for 5h to obtain the aged cerium-zirconium composite oxide.
Experimental example 1
The surface element contents of the above examples and comparative examples were measured, respectively, and the results are shown in table 1 below.
TABLE 1 surface element contents of examples and comparative examples
From the results in table 1, it can be seen that the doped rare earth elements in the cerium-zirconium composite oxide provided by the present invention are reduced or increased by not more than 5% compared with the fresh state after aging at 1100 ℃ for 5 hours. In other words, the doped rare earth elements are not basically precipitated from the composite oxide to the surface, and then the high-temperature stability and the catalytic performance of the cerium-zirconium composite oxide are improved.
Experimental example 2
The specific surface area, pore volume, grain size and static oxygen storage amount of the above examples and comparative examples were measured, respectively, and the results are shown in table 2 below.
TABLE 2 indexes of composite oxides
As can be seen from the results in table 2, the cerium-zirconium composite oxide provided by the present invention has excellent high temperature stability and catalytic performance, and all indexes thereof are excellent.
In summary, the invention provides a high temperature resistant cerium-zirconium composite oxide and a preparation method thereof. After being aged at the high temperature of 1100 ℃, the doped rare earth elements are not separated out from the cerium-zirconium composite oxide to the surface, so that the cerium-zirconium composite oxide catalyst has excellent high-temperature stability and can meet the requirement of the catalyst for purifying the automobile exhaust. According to the cerium-zirconium composite oxide prepared by the method combining fractional precipitation and hydrothermal reaction, on one hand, precipitation of rare earth elements from the cerium-zirconium composite oxide can be inhibited by changing the precipitation sequence, and the high-temperature stability and catalytic performance of the cerium-zirconium composite oxide can be obviously improved; on the other hand, through hydrothermal reaction, the crystal grains of the cerium-zirconium composite oxide can be well grown in the initial stage, the grain boundary energy is reduced, so that good thermal stability is kept, and meanwhile, under the condition of high pressure, the doped rare earth elements can well enter the cerium-zirconium crystal lattice to form the composite oxide, so that the high-temperature stability of the composite oxide is improved.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (9)
1. A cerium-zirconium composite oxide characterized by consisting of a cerium oxide, a zirconium oxide, and at least one oxide of a rare earth metal element other than cerium; the cerium-zirconium composite oxide has the following surface element contents in a fresh state:
25-50 wt% of cerium element;
20-65 wt% of zirconium element;
0-10wt% of lanthanum element;
0-10wt% of yttrium element;
0-20wt% of neodymium element;
0-20wt% of praseodymium element;
wherein, the contents of lanthanum element, yttrium element, neodymium element and praseodymium element are not 0 at the same time;
after the cerium-zirconium composite oxide is aged and heat-treated at 1100 ℃ for 5 hours, the content of the doped rare earth elements on the surface of the cerium-zirconium composite oxide is reduced, unchanged or increased compared with the content of the doped rare earth elements in a fresh state, and the increase amplitude is not more than 5%;
the cerium-zirconium composite oxide has a specific surface area of 30m or more after being aged and heat-treated at 1100 ℃ for 5 hours2G and/or pore volume of 0.25cm or more3/g;
The cerium-zirconium composite oxide has a grain size of 12nm or less after being subjected to aging heat treatment at 1100 ℃ for 5 hours;
the preparation method of the cerium-zirconium composite oxide comprises the following steps:
(a) first-step precipitation: dissolving corresponding rare earth element salt in mass of oxide in pure water, and then carrying out contact reaction on the obtained solution and excessive alkali liquor to obtain precipitation slurry A of the rare earth element; the rare earth element does not include cerium;
(b) the first step is hydrothermal: carrying out hydrothermal reaction on the obtained precipitation slurry A to obtain slurry B;
(c) and a second step of precipitation: dissolving cerium salt and zirconium salt corresponding to the mass of oxides in pure water, and carrying out contact reaction with the obtained slurry B to obtain a precipitate slurry C;
(d) the second step is hydrothermal: carrying out hydrothermal reaction on the obtained precipitation slurry C to obtain slurry D; and adding a surfactant into the slurry D, fully stirring, and then carrying out solid-liquid separation, washing and roasting to obtain the cerium-zirconium composite oxide.
2. The cerium-zirconium composite oxide according to claim 1, wherein the cerium-zirconium composite oxide has a specific surface area of 60m or more after aging heat treatment at 1000 ℃ for 5 hours2G and/or pore volume of 0.45cm or more3(ii)/g; and/or the presence of a gas in the gas,
after the cerium-zirconium composite oxide is aged and heat treated at 1100 ℃ for 5 hours, the static oxygen storage amount is more than or equal to 600 mu mol O2/g。
3. The cerium-zirconium composite oxide according to claim 1 or 2, wherein the doped rare earth element is contained in an amount of 0 to 30wt% on the surface of the cerium-zirconium composite oxide after aging heat treatment at 1100 ℃ for 5 hours.
4. The cerium-zirconium composite oxide according to claim 1 or 2, wherein the cerium-zirconium composite oxide has a surface element content of, after aging heat treatment at 1100 ℃ for 5 hours:
25-50 wt% of cerium element;
20-65 wt% of zirconium element;
0-10wt% of lanthanum element;
0-10wt% of yttrium element;
0-20wt% of neodymium element;
0-20wt% of praseodymium element.
5. The method for producing a cerium-zirconium composite oxide according to any one of claims 1 to 4, which comprises:
(a) first-step precipitation: dissolving corresponding rare earth element salt in mass of oxide in pure water, and then carrying out contact reaction on the obtained solution and excessive alkali liquor to obtain precipitation slurry A of the rare earth element; the rare earth element does not include cerium;
(b) the first step is hydrothermal: carrying out hydrothermal reaction on the obtained precipitation slurry A to obtain slurry B;
(c) and a second step of precipitation: dissolving cerium salt and zirconium salt corresponding to the mass of oxides in pure water, and carrying out contact reaction with the obtained slurry B to obtain a precipitate slurry C;
(d) the second step is hydrothermal: carrying out hydrothermal reaction on the obtained precipitation slurry C to obtain slurry D; and adding a surfactant into the slurry D, fully stirring, and then carrying out solid-liquid separation, washing and roasting to obtain the cerium-zirconium composite oxide.
6. The method according to claim 5, wherein the temperature of the first precipitation is 30 to 80 ℃.
7. The preparation method according to claim 5, characterized in that the temperature of the first step hydrothermal is 90-220 ℃ and the time is 6-48 h; and/or the presence of a gas in the gas,
the hydrothermal temperature of the second step is 90-250 ℃ and the hydrothermal time is 6-48 h.
8. The method according to claim 5, wherein the surfactant is selected from the group consisting of a cationic surfactant, an anionic surfactant, and a nonionic surfactant.
9. Use of a catalyst prepared from the cerium zirconium composite oxide according to any one of claims 1 to 4 or a catalyst prepared from the cerium zirconium composite oxide prepared by the method according to any one of claims 5 to 8, for purification of exhaust gas from automobiles, catalytic combustion of natural gas, purification treatment of organic exhaust gas, or denitration treatment of industrial exhaust gas.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110834188.XA CN113275000B (en) | 2021-07-23 | 2021-07-23 | High-temperature-resistant cerium-zirconium composite oxide and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110834188.XA CN113275000B (en) | 2021-07-23 | 2021-07-23 | High-temperature-resistant cerium-zirconium composite oxide and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113275000A CN113275000A (en) | 2021-08-20 |
CN113275000B true CN113275000B (en) | 2021-11-09 |
Family
ID=77287153
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110834188.XA Active CN113275000B (en) | 2021-07-23 | 2021-07-23 | High-temperature-resistant cerium-zirconium composite oxide and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113275000B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117509724A (en) * | 2023-09-28 | 2024-02-06 | 江门市科恒实业股份有限公司 | Cerium-zirconium composite oxide and preparation method thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1255105A (en) * | 1997-04-04 | 2000-05-31 | 罗狄亚稀土公司 | Cerium oxides, zirconium oxides, Ce/Zr mixed oxides and Ce/Zr solid solutions having improved thermal stability and oxygen storage capacity |
CN1552517A (en) * | 2003-12-19 | 2004-12-08 | 广东工业大学 | Preparation of nano cerium-zirconium rare-earth composite fluorine compound solid solution based catalyst |
EP1632288A1 (en) * | 2004-09-03 | 2006-03-08 | Mazda Motor Corporation | Exhaust gas purification catalyst and oxygen storage component for the same |
CN1962051A (en) * | 2005-11-10 | 2007-05-16 | 北京有色金属研究总院 | Solid solution composition of cerium zirconium compound oxide with high specific surface and method for preparing the same |
CN110327909A (en) * | 2019-06-11 | 2019-10-15 | 山东国瓷功能材料股份有限公司 | A kind of preparation method of high oxygen storage capacity cerium zirconium compound oxide |
CN110366445A (en) * | 2016-12-23 | 2019-10-22 | 罗地亚经营管理公司 | The anti-aging mixed oxide made of cerium, zirconium, aluminium and lanthanum for motor vehicles catalytic converter |
CN110385120A (en) * | 2019-06-19 | 2019-10-29 | 山东国瓷功能材料股份有限公司 | A kind of cerium zirconium compound oxide and preparation method thereof |
-
2021
- 2021-07-23 CN CN202110834188.XA patent/CN113275000B/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1255105A (en) * | 1997-04-04 | 2000-05-31 | 罗狄亚稀土公司 | Cerium oxides, zirconium oxides, Ce/Zr mixed oxides and Ce/Zr solid solutions having improved thermal stability and oxygen storage capacity |
CN1552517A (en) * | 2003-12-19 | 2004-12-08 | 广东工业大学 | Preparation of nano cerium-zirconium rare-earth composite fluorine compound solid solution based catalyst |
EP1632288A1 (en) * | 2004-09-03 | 2006-03-08 | Mazda Motor Corporation | Exhaust gas purification catalyst and oxygen storage component for the same |
CN1962051A (en) * | 2005-11-10 | 2007-05-16 | 北京有色金属研究总院 | Solid solution composition of cerium zirconium compound oxide with high specific surface and method for preparing the same |
CN110366445A (en) * | 2016-12-23 | 2019-10-22 | 罗地亚经营管理公司 | The anti-aging mixed oxide made of cerium, zirconium, aluminium and lanthanum for motor vehicles catalytic converter |
CN110327909A (en) * | 2019-06-11 | 2019-10-15 | 山东国瓷功能材料股份有限公司 | A kind of preparation method of high oxygen storage capacity cerium zirconium compound oxide |
CN110385120A (en) * | 2019-06-19 | 2019-10-29 | 山东国瓷功能材料股份有限公司 | A kind of cerium zirconium compound oxide and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN113275000A (en) | 2021-08-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1872851B1 (en) | Cerium oxide-zirconium oxide-based mixed oxide and method for the production thereof | |
EP0963951B1 (en) | Cerium- and zirconium-based mixed oxide, method of producing same and catalyst material for exhaust gas purification | |
JP3623517B2 (en) | Composition based on cerium oxide and zirconium oxide and having high specific surface area and high oxygen storage capacity, and method for producing the same | |
JP4328338B2 (en) | Catalyst for exhaust gas purification of internal combustion engine | |
US20030186805A1 (en) | Ceria-based mixed-metal oxide structure, including method of making and use | |
CN101300071A (en) | Catalyst for exhaust gas clean-up | |
JPWO2003022740A1 (en) | Cerium oxide, its production method and exhaust gas purifying catalyst | |
KR102371855B1 (en) | Cerium- and zirconium-based mixed oxides | |
CN111939894A (en) | Cerium-zirconium-based composite oxide with core-shell structure and preparation method thereof | |
CN110026179B (en) | Cerium-zirconium composite oxide with high oxygen storage capacity and preparation method thereof | |
US10258964B2 (en) | Composite oxide | |
JP2003277059A (en) | Ceria-zirconia compound oxide | |
CN113275000B (en) | High-temperature-resistant cerium-zirconium composite oxide and preparation method and application thereof | |
JP4352300B2 (en) | Composite oxide, method for producing the same, and co-catalyst for exhaust gas purification | |
JP4450763B2 (en) | Precious metal-containing composite metal oxide for exhaust gas purification catalyst and method for producing the same | |
JP4972868B2 (en) | Surface-modified ceria / zirconia hydrated oxide, oxide thereof, production method thereof, and use thereof | |
EP2905260A1 (en) | Method for producing composite oxide and composite oxide catalyst | |
JPH0780311A (en) | Catalyst for purification of exhaust gas | |
EP1928788B1 (en) | Method for preparing metal oxide containing precious metals | |
JP2006256911A (en) | Preparation method of ceria-zirconia-based oxide | |
JP2008230937A (en) | Compound oxide and compound oxide carrier, and method for producing catalyst for exhaust gas clarification using them | |
JP4811666B2 (en) | Composite particle precursor aqueous solution for producing NOx occlusion reduction type catalyst and method for producing NOx occlusion reduction type catalyst using the same | |
JP2004181435A (en) | Heat-resistant compound oxide, exhaust gas cleaning catalyst and production method for the same | |
JP2004283775A (en) | Carbon monoxide selective oxidation catalyst composition | |
JP2019189484A (en) | Oxygen storage material and manufacturing method therefor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |